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Патент USA US2111469

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2,111,469
Patented Mai-.,15,',193's _
UNITED STATES PATEN’TQOFFICE ‘
MANUFACTURE OF FORMALDEHYDE
.
\
Jacques Franc-on, Paris, France
No Drawing. Application December 31, 1935, Se
rial No. 57,063. In Great Britain January 5,
1935 >
10 Claims.
(01. 260—138)
This invention relates to the manufacture of and heated to at least 100° C., whereby the nickel
formaldehyde from carbon monoxide and hydro ' tetra-carbonyl is decomposed
gen ’or gases containing them and has particular
reference to the joint action of heat and catalytic
.5 material on a mixture of the gases when freed
from impurities.
x
According to the present invention, the mix
ture of reaction gases-whether puri?ed in any
known way or by means of the special puri?er or
10 puri?ers above described-45 subjected to the
and the nascent metal becomes deposited on the 5
coils.
,
'
-
.
An alternative and preferable way of preparing
the’ catalytic material isto pro-oxidize the surface of the supporting metal coils or gauzes by
treating them in the presence of air and then to 10
action of a catalyst consisting of porous or ?nely - mix them thoroughly with a nickel hydroxide
divided nickel particles carried-0n a metal sup
port and aided in their catalytic action by a
small amount of another metal as promoter.
A.
15 convenient metal support, is of nickel, chromium
or aluminium in the vform of single or multiple
coiled spiral strips of coiled-up gauze or the like
presenting a large surface per unit of volume
‘ occupied.
A convenient size of strip from which
20 to make a coil is one about 50 to 100 mms. long
and about‘20 to 35 mms. wide. In addition to
paste and subject the mixtureI to the prolonged
action of a current of dry hydrogen at a tem
perature of about 240° C. to 280° C. for at least
40 to 60 hours, preferably 100 hours or more, 15/
whereby the nickel hydroxide is reduced to metal
in the desired physical state.
The amount of nickel paste mixed with the
support is preferably such that after reduction
the ratio of support to reduced nickel is about
9 to 1 in ‘weight.
'
'
20
‘ “The nickel hydroxide paste may be pre
amounts, say 1 to 5 per cent. of any or all of the pared in any vconvenient manner 'as for .ex
- ample by treating pure nickel powder, wire.
the nickel it is advantageous to employ small
following metals: silver, vanadium, cobalt, cope
25 per and cadmium or alloys thereof.
~
In order to obtain‘ the best results the above
mentloned catalytic material should be packed
by preference in a vertical chamber or tube or
or fragments with diluted pure nitric acid,
?ltering, diluting the nickel nitrate solution, 25
‘adding aqueous caustic soda until there is
a slight alkaline reaction to litmus paper, al
lowing to stand, decanting by syphon the super
group of chambers or tubes about 6 metres high. _ natant liquid. containing the sodium nitrate, add
30 maintained at a temperature ranging from 180°
to 225° C. vaccording to the composition of the
gaseous mixture to be treated, the more the hy
drogen present in the mixture‘ the lower being
3 "it the temperature adopted.
temperatures. The
catalytic
materialsv
should be prepared in one or other of the follow
40 ing ways:-
.
_
One way of preparing the catalytic material
with the nickel in the desired porous or ?nely
divided state is to expose the supporting metal to
a stream of the vapors of an organo-nickel com
-
4
ing—if necessary with the aid of a vacuum or
pressure,—_to give a suitable degree of pastiness
It may be advisable ' to the mass.p
in certain cases to pass the gases through two
catalytic chambers or zones maintained'at‘dif
ent
ing water, agitating, and decanting repeatedly to 30
well wash the nickel hydroxide, and ?nally ?lter
pound under conditions which decompose the
vapors and cause the nickelcomponent to be de
' posited.‘ For this purpose reduced nickel may
- ?rst be exposed at a temperature of about
50 50° C. to a current of carbon monoxide whereby
nickel tetracarbonyl (Ni(CO)4)
is produced
which is carried off as a vapor by excess, of the
At this stage it is desirable to add
from '1 to 5 per cent. by weight of the hydroxides 00 5
of silver, vanadium,rcobalt, cadmium and cop
per or of hydroxide mixtures derived from their
alloys as already stated, preferably by precipi
tation from the nitrates by means of caustic soda.
The paste is then mixed with the preoxidized 0
metal support and reduced as already described.
The mixture of carbon mohoxideand hydrogen
or gases containing at least 30 per cent. of hy
drogen, if requiring puri?cation, especially for
removal of sulphur or sulphur- compounds, is 4"
passed through one or more puri?ers. A suit
able form of puri?er consists of a tube or cham
ber or a group of tubes or chambers of sum
cient length to ensure that the whole of the gases
will have contacted with the purifying material
before they leave. A satisfactory length for this
0
purpose is 6 metres. These tubes or chambers
carbon-monoxide stream. _ These mixed gases
contain layers or columns of iron, copper and
and vapors are then directed over the above-men
55 tioned supporting metal coils enclosed in a space nickel in the order named and preferably in 66
2
2,111,469
the form of single or multiple coiled spiral strips,
if desired pressures higher than atmosphericmay
wires or coiled up gauze or the like, presenting
a large surface per unit of volume occupied and
arranged for contact in the order stated. These
materials may or may not be mixed with a small
be employed.
amount of nickel paste as indicated hereafter.
It is preferable and in certain cases necessary,
where the gases to be puri?ed contain sulphur
compounds, to pass the gases through two dif
10 ferent puri?ers in series; in which 'case the sec
ond purifying tube or chamber or group of tubes
or chambers, about 6 metres long, contain a com
'
What I claim is:
1. The method of producing formaldehyde
from carbon monoxide and hydrogen which com
prises bringing a mixture of carbon monoxide and
hydrogen, freed from catalyst poisons, at a tem
perature ranging from about 180° C. to about
225° C. into contact with catalytic material con
sisting of nickel particles deposited on a metal 10
support and aided in their catalytic action by
a small amount of a metal promoter taken from
position of ?ne particles of copper very thorough
ly and widely dispersed ina highly porous form
of carbon resulting from calcining in situ the
material known as cuprene obtainable by treat
ing ?nely divided copper or copper oxide with
the group consisting of silver, vanadium, cobalt,
cadmium and copper.
2. The method of producing vformaldehyde
from carbon monoxide and hydrogen which com
prises bringing a mixture of carbon monoxide
and hydrogen, freed from catalyst poisons, at a
acetylene, which as is known greatly swells espe
cially in response to a repeated treatment and
temperature ranging from about 180° C. to about
225° C. into contact with catalytic material con 20
sisting of nickel particles deposited on a metal
support consisting of a metal taken from the
group consisting‘ of nickel, chromium and alu
minum and aided in- their catalytic action by a
small amount of a metal promoter taken from 25
20 at a temperature of about 200 to 280° C. or even
higher, for example about 350° C.
In certain cases it may be desirable to add to
this cuprene a similar material produced in the
25 same way from nickel or cobalt and which may
be termed “nicrene” to “cobrene” respectively.
Either of these materials may be mixed with
a small quantity of nickel paste referred to here’
inafter and the total mixture thoroughly mixed
the group consisting of silver, vanadium, cobalt,
cadmium and copper.
_
3. The method of producing formaldehyde
from carbon monoxide and hydrogen which com~
30 with wood charcoal as a carrier.
The series of puri?ers are advantageously ar
prises bringing a mixture of carbon monoxide 30
and hydrogen, freed from catalyst poisons, at a
temperature ranging from about 180° C. to about
225° C. into contact with catalytic material con
sisting of nickel particles deposited on a metal
support and aided in their catalytic action by 1 35
to 5% of a metal promoter taken from the group
ranged in duplicate,—one being in purifying ac
tion while the other-which has become charged
with impurities in the course of a previous oper
ation—-is being reduced and freed from accumu
lated impurities~the ?rst series being reactivat
ed by means of air and the second by means of
steam passed through in the reverse direction to
the direction in which the reacting gases had
passed. In the case of a puri?er containing iron,
consisting of silver, vanadium, cobalt, cadmium
and copper.
4. The method of producing formaldehyde from
carbon monoxide and hydrogen which comprises 40
copper and nickel in the order named as already
described, it is maintained at a temperature of
bringing a mixture of carbon monoxide and hy
drogen, freed from catalyst poisons, at a tem
?er packed with calcined cuprene, “nicrene” or perature ranging from 180 to 225° C. into con
“cobrene”, it is maintained also at a tempera— tact with catalytic material consisting of nickel
ture of about 300 to 350° C. The puri?ed gases particles deposited on a metal support consist 45
coming from the puri?er or puri?ers are then ing of a metal taken from the group consisting of
passed at substantially atmospheric pressure nickel, chromium. and aluminum and aided in
through the above described catalyst chamber or their catalytic action by 1 to 5% of a metal‘ pro
£50 tube or nest of tubes about 6 metres long main- - moter taken'from the group consisting of silver,
50
tained at a temperature between 180 and 225° C. vanadium, cobalt, cadmium and copper.
Frequent regenerationof the catalyst is neces
5. A catalyst for use in the production of
sary and this may be effected either by passing formaldehyde from carbon monoxide and hy
the gaseous mixture for a short time, for exam
drogen, said catalyst consisting of ‘nickel particles
55 ple for a few minutes, over the catalytic mate-' deposited on a metal support, and a small amount
rial then interrupting the passage and reactivat
of a metal promoter taken from the group con 56
ing the catalyst by means of a current of a sisting of silver, vanadium, cobalt, cadmium and
suitable regenerating gas, or by employing a suit
copper for aiding the catalytic action of the
about 300 to 350° C. and in the case of a puri
able reactivating gas together with the reacting
nickel particles.
gases so as to cause regeneration simultaneously '
with the production of ‘the formaldehyde. The
reactivating gases employed may be nitrogen or
oxides of nitrogen or any other gas, e. g. carbon
dioxide, hydrogen or water vapor, not forming
85 a stable compound with the catalytic material.
Water vapor is particularly suitable for use as ‘
a reactivating gas together with the _reacting
gases.
As an example, when a mixture of carbon mon
oxide and hydrogen ‘is-passed at a velocity of one
metre per second over the catalyst, the time of
reaction may be two minutes, followed by a period
of reactivation of forty seconds. The reaction is
76 preferably effected at atmospheric pressures, but
_
formaldehyde from carbon monoxide and hy 60
drogen, said catalyst consisting of nickel particles
deposited on a, metal support consisting of a
metal taken from the group consisting of nickel,
chromium and aluminum, and a small amount of
ametal promoter taken from the group consisting 65
of silver, vanadium, cobalt, cadmium and copper
for aiding the catalytic action of the nickel par
'
'
70
'
6. A catalyst for use in the production of
ticles.
7. A catalyst for use in the production of
formaldehyde from carbon monoxide and hy 70
drogen, said catalyst consisting of nickel particles
deposited on a metal support consisting of a
metal taken from the group consisting of nickel,
chromium and aluminum, and 1 to 5% of a 75
Want
metal promoter taken from the group consisting
of silver, vanadium, cobalt, cadmium and copper
for aiding the catalytic action of the nickel par
ticles.
‘
_
'
8. The method of producing formaldehyde from
carbon monoxide and hydrogen which comprises
bringing a mixture of carbon monoxide and hy
drogen, freed from catalyst poisons, at. a tem
perature ranging from about 180"v C. to about 225°
10 G. into contact with catalytic material consisting
oi nickel particles deposited on a metal support
and aided in their catalytic action by a small
amount of a metal promoter taken from the group
consisting of silver, vanadium, cobalt, cadmium
15 and copper, and discontinuing the production in
termittently in order to reactivate the catalyst by
means of a regenerating gas.
,
9. The method of producing formaldehyde from
carbon monoxide and hydrogen which'comprises
20 bringing a mixture of carbon monoxide and hy
drogen,'ireed from catalyst poisons, at a tem
perature ranging from about 180° C. to about 225°
'
.
. Y
It
(2. into contact with catalytic material'consist
ing of nickel particles deposited on a metal sup
port and aided in their catalytic action by a
small amount of a metal promoter taken from the
group consisting of silver, vanadium, cobalt,
cadmium and copper, and adding a regenerat
ing gas to the gaseous reaction mixture so as to
regenerate simultaneously with the main reac
tion.
'
.
l
,
.
10. The method of producing formaldehyde
from carbon monoxide and hydrogen which com
10
prises bringing a mixture of carbon monoxide and
hydrogen, i'reed from. catalyst poisons, at a tem
perature ranging from about 180° C. to about 225°
G. into contact with catalytic material consisting 15
of nickel particles deposited on a metal support
I and aided in their catalytic action by a small
amount of a metal promoter taken from the group
consisting of silver, vanadium, cobalt, cadmium
and copper, and reactivating the catalyst by means 20
of a regenerating gas.
JACQUES FRANGON.
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